Optical shutter

ABSTRACT

The present invention pertains to an optical shutter comprising an organic free compound, such as a radical cation or a radical anion, and a polydiacetylene compound, wherein the polydiacetylene compound is characterized by having a change in absorption in a wavelength region as a result of a photo-induced heat transfer from the free radical compound. The thermochromic change in absorption is reversed by thermal cooling or by a photo-induced reaction after the photo-induced heat transfer. Also provided is an optical shutter for use as an optical switch in fiber optic communications, and, alternatively, for use in a laser protection device, in a security protection system, or in an eyewear device.

RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional PatentApplication No. 60/197,726, filed Apr. 18, 2000, the contents of whichare fully incorporated herein by reference for all purposes.

FIELD OF THE INVENTION

[0002] The present invention relates to the field of optical shuttersand, particularly, pertains to optical shutters which operate in thenear-infrared and/or visible wavelength regions. More specifically, thisinvention pertains to optical shutters comprising one or more photonabsorbing materials, such as an organic free radical compound thatconverts absorbed photons to heat in less than 1 nanosecond, and one ormore reversible thermochromic polydiacetylene materials.

BACKGROUND OF THE INVENTION

[0003] Throughout this application, various publications, patents, andpublished patent applications are referred to by an identifyingcitation. The disclosures of the publications, patents, and publishedpatent specifications referenced in this application are herebyincorporated by reference into the present disclosure to more fullydescribe the state of the art to which this invention pertains.

[0004] As the quantity and speed of data communications over fiberoptics systems rapidly increases due to the growing demand from Internetusage and other communications, all-optical switching systems are ofincreased interest to overcome the high cost and slow switching speedsof conventional switches. These conventional switches include, forexample, various mechanical switches, electro-optic switches, andthermo-optic switches, such as, for example, described in U.S. Pat. Nos.5,732,168 and 5,828,799, both to Donald. In particular, the increasedcomplexity and cost of switching systems which involve switching from anoptical signal to an electrical signal and then back to an opticalsignal have increased the level of interest in all-optical switches.

[0005] An all-optical switch typically switches an optical signal fromone output port to another. This is typically accomplished by applyingan input pump signal from a pump laser source to cause the opticalsignal to be selectively switched. The switch is responsive to the laserpump signal to selectively switch the light of the optical signal to oneor the other of the output ports.

[0006] A variety of approaches are known for making all-optical orhybrid optical switches, such as, for example, described in U.S. Pat.No. 5,905,587 to Maeno et al.; U.S. Pat. No. 5,923,798 to Aksyuk et al.;U.S. Pat. No. 5,970,185 to Baker et al.; U.S. Pat. No. 5,841,912 toMueller-Fiedler et al.; U.S. Pat. No. 5,757,525 to Rao et al.; U.S. Pat.No. 5,872,648 to Sanchez et al.; U.S. Pat. No. 5,091,984 to Kobayashi etal.; U.S. Pat. No. 5,406,407 to Wolff; U.S. Pat. No. 5,740,287 toScalora et al.; U.S. Pat. No. 5,960,133 to Tomlinson; and U.S. Pat. No.5,539,100 to Waslielewski et al. For example, as described in U.S. Pat.No. 5,943,453 to Hodgson, one basic configuration for an all-opticalswitch is a Mach-Zehnder interferometer which includes a first fiberoptic input arm for receiving an input optical signal and a second fiberoptic input arm for receiving a switching pump signal. The input armsare fused together to form a first coupler which subsequently branchesout into two intermediate arms. The first coupler splits the input lightsignal into equal portions which then enter the two intermediate arms.The two intermediate arms are once again fused to form a second couplerwhich branches into two output arms. After traveling through the twointermediate arms, the two signals are recombined by the second coupler.If the two signals are in phase at the second coupler, then all thelight is coupled into a first one of the two output ports. If the twosignals are completely out of phase, then the light is coupled into theother of the two output ports. The reliability of the Mach-Zehnderinterferometer for optical switching is typically sensitive totemperature-dependent effects.

[0007] The need for improved optical switches is increased by the use ofwavelength add/drop multiplexing (WADM) which converts the opticalsignal in the optical fiber into, for example, 16 signals at 16different wavelengths in a near-infrared range of about 1540 to 1560 nm,as, for example, described in Bell Labs Technical Journal, January-March1999, pages 207 to 229, and references therein, by Giles et al.; and inU.S. Pat. No. 5,959,749 to Danagher et al. There is about 1 nm betweenthe wavelength channels. The primary function of the optical switch isto add and/or drop optical signals from the multiple wavelengthstraveling through the optical fiber. It would be highly desirable tohave arrays of optical switches to handle the optical signals frommultiple wavelengths per optical fiber and multiple optical fibers, suchas up to 100×100 or greater optical switch arrays. Also, it would behighly desirable if the response time for the optical switch isultrafast, such as 1 nanosecond or less.

[0008] It would be advantageous if an all-optical switching system wereavailable which avoided the complexity and cost of hybrid electro-opticand other systems while increasing the speed of the switching times fromthe millisecond range to the nanosecond or picosecond ranges.

SUMMARY OF THE INVENTION

[0009] One aspect of the present invention pertains to an opticalshutter comprising (1) an organic free radical compound in which thefree radical compound is photonabsorbing and (2) a polydiacetylenecompound, wherein the polydiacetylene compound is characterized byhaving a change in absorption in a wavelength region as a result of aphoto-induced heat transfer from the free radical compound. In oneembodiment, the free radical compound is a radical cation, preferably anaminium radical cation. In one embodiment, the free radical compound isa radical anion, preferably an anthrasemiquinone radical anion.

[0010] In one embodiment of the optical shutter of this invention, thechange in absorption is reversed by cooling to a temperature of lessthan 50° C. In one embodiment, the change in absorption is reversed bycooling to a temperature of less than 75° C. In one embodiment, thechange in absorption is reversed by cooling to a temperature of lessthan 110° C.

[0011] In one embodiment of the optical shutter of this invention, thechange in absorption as a result of the photo-induced heat transfer isreversed by a photo-induced reaction. In one embodiment, the opticalshutter comprises a photosensitizer compound and the photo-inducedreaction is sensitized by the photosensitizer compound. In oneembodiment, the photo-induced reaction is a photo-induced reversibleelectron transfer reaction.

[0012] In one embodiment of the optical shutter of the presentinvention, the optical shutter is utilized in an optical switch for afiber optics communications channel. In one embodiment, the opticalshutter is utilized in a viewing lens of an eyewear device. In oneembodiment, the optical shutter is utilized in a laser protection devicefor protection of eyes or sensors from a source of laser radiation. Inone embodiment, the optical shutter is utilized in a security protectionsystem based on detecting the change in absorption upon exposure of theoptical shutter in the security protection system to high intensityradiation selected from the group consisting of ultraviolet radiation,visible radiation, and infrared radiation.

[0013] As will be appreciated by one of skill in the art, features ofone aspect or embodiment of the invention are also applicable to otheraspects or embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0014] The optical shutters of the present invention provide superiorspeed of response, such as a response time of 1000 picoseconds or less,to the incident radiation, and are particularly useful in systems wherean all-optical shutter or switch mechanism is desirable.

[0015] An organic free radical compound where the excited state is anexcited state corresponding to a free radical ground state to an excitedstate absorption transition may have a rapid internal conversion fromthis excited state back to the ground state with a concomitantproduction of heat in a time scale of as low as 1 picosecond or less. Inone example of this, a photon absorbing material absorbs photons in thepresence of a thermochromic compound, converts the absorbed photons toheat in less than 1 nanosecond, and causes a change in absorption due toheat-induced changes in the thermochromic compound, as described in PCTInternational Publication No. WO 98/54615, titled “Optical ShutterDevice” and published Dec. 3, 1998, by Carlson. The present inventionutilizes a polydiacetylene compound which undergoes a heat-inducedreversible thermochromic transformation which causes changes inabsorption. This heat-induced reaction may occur faster than internalconversion of the absorbed photons to heat or, alternatively, may have asimilar or lower speed than this internal photon-to-heat conversion toheat by the organic free radical compound.

Organic Free Radical Compounds

[0016] The term “organic free radical compounds,” as used herein,pertains to organic compounds which comprise at least one free unpairedelectron on an atom, such as, for example, a carbon atom, a nitrogenatom, or an oxygen atom, in the ground state of the organic compound.Suitable organic free radical compounds for the optical shutters of thepresent invention include neutral organic free radicals, organic freeradical cations, and organic free radical anions. For purposes ofbrevity, the terms “organic free radical cation”, “organic radicalcation”, and “radical cation” are used interchangeably herein. The word“cation,” as used herein, pertains to a positively charged atom in amolecule, such as, for example, a positively charged nitrogen atom.Similarly, the terms “organic free radical anion”, “organic radicalanion”, and “radical anion” are used interchangeably herein. The word“anion,” as used herein, pertains to a negatively charged atom in amolecule, such as, for example, a negatively charged oxygen atom. Itshould be noted that the free unpaired electron and the positive andnegative charges of the organic free radical compounds may be localizedon a single atom or shared among more than one atom.

[0017] Examples of suitable organic free radical cations for the opticalshutters of this invention include, but are not limited to, aminiumradical cations, such as, for example, tris (p-dibutylaminophenyl)aminium hexafluoroantimonate, which is commercially available as IR-99,a trademark for a dye available from Glendale Protective Technologies,Inc., Lakeland, Fla. IR-99 is known to be a stable radical cation thatmay exist in a layer of material, such as in a polymeric coating, undernormal room conditions for an extended period of time. Another exampleof a useful aminium radical cation is IR-126, a trademark for a dyeavailable from Glendale Protective Technologies, Inc., Lakeland, Fla.Another useful radical cation is IR-165, a trademark for a dye availablefrom Glendale Protective Technologies, Inc., Lakeland, Fla. IR-165 is astable diradical dication which may be formed by a one-electronoxidation of IR-126. A wide variety of anions may be utilized with theradical cations as, for example, the anions described in U.S. Pat. No.6,214,435 B1 to Onishi et al. and references therein.

[0018] Examples of suitable organic free radical anions for the opticalshutters of the present invention include, but are not limited to,anthrasemiquinone radical anions, such as, for example, described inPhotochemistry and Photobiology, Vol. 17, pages 123-131 (1973), byCarlson et al.

[0019] Due to the presence of the free radical moiety, organic freeradical compounds typically have unique longer wavelength absorptionswhen compared to the corresponding non-free radical compounds. Forexample, the absorption spectra of IR-165, a radical cation, and itsextremely rapid internal conversion of absorbed photons to heat aredescribed in various publications, such as in PCT InternationalPublication No. WO 98/54615, and references therein, to Carlson. Also,for example, the absorption spectra of 9,10-anthrasemiquinone radicalanion and its photochemistry are described in the above-referencedpublication by Carlson et al. and in The Photochemistry of Anthraquinoneand Related Compounds, Ph.D. Thesis, Massachusetts Institute ofTechnology, 1969, by Carlson.

[0020] An organic free radical compound where the excited statecorresponds to a lowest excited state formed directly from absorptionfrom the free radical ground state may have a rapid conversion from thisexcited state back to the ground state with an accompanying productionof heat by this photothermal process in a time scale of as low as 1picosecond or less, as, for example, observed with coatings of IR-165upon high intensity laser irradiation at 1065 nm, as described, forexample, in PCT International Publication No. WO 98/54615, andreferences therein, to Carlson. The present invention is directed atutilizing organic free radical compounds and, alternatively, non-freeradical compounds, that undergo a very rapid photo-induced heat transfertogether with a reversible thermochromic material, such as athermochromic polydiacetylene compound, for use in an optical shutterwhere the desired change in absorption upon optical excitation is aresult of a reversible thermochromic transformation.

[0021] For example, a light yellow-green layer comprising IR-165 uponlaser exposure at 1065 nm undergoes photo-induced heat transfer whichefficiently heats the layer to elevated temperatures as high as, forexample, 500° C. The presence of a reversible thermochromicpolydiacetylene compound in the layer produces a product having areversible change in absorption in the visible and/or the near-infraredwavelength regions.

[0022] Also, for example, layers comprising anthrasemiquinone radicalanions, including the many possible substituted and other derivatives ofthe anthrasemiquinone radical anion, may undergo photo-induced heattransfer which occurs very rapidly and efficiently heats the layer toelevated temperatures. The presence of a reversible thermochromicpolydiacetylene compound in the layer produces a product having areversible change in absorption in the visible and/or the near-infraredwavelength regions.

Polydiacetylene Compounds

[0023] The term “polydiacetylene compounds”, as used herein, pertains topolymeric compounds which comprise at least one conjugated diacetylenicmoiety of two triple-bonded acetylenic moieties joined together througha carbon-carbon single bond. Suitable polydiacetylene compounds for theoptical shutters of the present invention are thermochromic with areversible thermochromic process upon heating and subsequent cooling, asknown in the art for polydiacetylene compounds, or alternatively athermochromic process upon heating that may be reversed by aphoto-induced reaction, such as by a photo-induced reversible electrontransfer reaction. Many polydiacetylenes show thermochromic properties,but the thermochromic transition is often irreversible and the colorformed upon heating is permanent. For example, a typical color for apolydiacetylene compound is blue. Upon heating, this blue colortypically undergoes a thermochromic change to red. For example, for areversible thermochromic polydiacetylene compound that changes from blueto red upon heating, such as with heating to a temperature of 70° C.,subsequent cooling to below 70° C., such as to around 25° C., changesthe color back to blue. This reversible thermochromic behavior may berepeated through many heating-cooling cycles.

[0024] By proper choice of molecular structure of the polydiacetylenecompound, the absorption spectrum of the non-heated and heatedreversible thermochromic forms may be matched to the wavelength regions,such as, a near-infrared wavelength, where an absorption change isdesired. Examples of reversible thermochromic polydiacetylene compoundsknown in the art, along with their absorption properties and molecularstructure and methods of synthesizing polydiacetylenes and ofincorporating polydiacetylenes into a layer, are described, for example,in U.S. Pat. No. 5,731,112, and references therein, to Lewis et al.;U.S. Pat. No. 5,508,145 to Robillard; U.S. Pat. No. 6,005,058 to Sandmanet al.; and U.S. Pat. No. 6,194,529 B1 to Hollingsworth et al.; and inLangmuir, Vol. 15, pages 3972-3980 (1999), and references therein, byHuo et al. For example, certain types of metal salts, such as zincsalts, of polydiacetylene compounds are described as reversible,thermochromic materials in U.S. Pat. No. 5,731,112, to Lewis et al.

Optical Shutters

[0025] One aspect of the present invention pertains to an opticalshutter comprising (1) an organic free radical compound in which thefree radical compound is photon-absorbing and is characterized byconverting absorbed photons to heat, preferably in less than 1nanosecond, and (2) a reversible thermochromic polydiacetylene compoundhaving a change in absorption in a visible and/or a near-infraredwavelength region as a result of a heat-induced transformation by aphoto-induced heat transfer from the free radical compound. The terms“near-infrared wavelength region” and “near-infrared”, as used herein,pertain to wavelengths from 700 nm to 2000 nm. The terms “visiblewavelength region” and “visible”, as used herein, pertain to wavelengthsfrom 400 to 700 nm. The terms “ultraviolet wavelength region” and“ultraviolet” as used herein, pertain to wavelengths from 200 to 400 nm.In one embodiment, the free radical compound is a radical cation,preferably an aminium radical cation, and most preferably, the radicalcation is tris (p-dibutylaminophenyl) aminium hexafluoroantimonate(TAH). In one embodiment, the free radical compound is a radical anion,preferably an anthrasemiquinone (ASQ) radical anion.

[0026] In one embodiment of the optical shutter of the presentinvention, the change in absorption is greater than 0.1, preferablygreater than 0.5, more preferably greater than 1.5, and most preferablygreater than 3.0. These absorption changes are measured in opticaldensity units, as known in the art, where an optical density of 1.0corresponds to 90% absorption and 10% transmission of the incidentwavelength or wavelengths of radiation. Thus, for example, an initialabsorption or optical density of the optical shutter of 0.1 at 1546 nmthat changes to an absorption or optical density in the optical shutterof 1.6 at 1546 nm would have a change in absorption of 1.6 minus 0.1 or1.5. In one embodiment, the near-infrared wavelength region of thechange in absorption is from 700 to 1000 nm. In one embodiment, thenear-infrared wavelength region of the change in absorption is from 1000to 1700 nm, preferably from 1250 to 1600 nm, and more preferably from1520 to 1580 nm.

[0027] In one embodiment of the optical shutter of this invention, thephoto-induced heat formation occurs in less than 1 nanosecond afterabsorption of photons by the free radical compound, preferably occurs inless than 0.1 nanoseconds, more preferably occurs in less than 0.01nanoseconds, and most preferably occurs in less than 0.001 nanoseconds.

[0028] In the optical shutter of this invention, the photo-inducedthermochromic change in absorption is reversible. In one embodiment, thechange in absorption is reversed by cooling to a temperature of lessthan 50° C. In one embodiment, the change in absorption is reversed bycooling to a temperature of less than 75° C. In one embodiment, thechange in absorption is reversed by cooling to a temperature of lessthan 110° C. In one embodiment, the change in absorption is reversed inless than 1 second after the photo-induced heat transfer, preferably isreversed in less than 10 milliseconds, more preferably is reversed inless than 1 millisecond, and most preferably is reversed in less than0.1 milliseconds. In one embodiment, the reversible change in absorptionoccurs at less than 50° C. In one embodiment, the reversible change inabsorption occurs at less than 75° C. In one embodiment, the reversiblechange in absorption occurs at less than 110° C. In one embodiment, thereversible change in absorption occurs in less than 1 second after thephoton absorption that produced the thermochromic transformation,preferably occurs in less than 10 milliseconds, more preferably occursin less than 1 millisecond, and most preferably occurs in less than 0.1milliseconds.

[0029] In addition to a thermal or dark reverse reaction to provide areversible change in absorption, the product of the photo-inducedthermochromic change in the polydiacetylene may be thermally stable, ormay be still present in the photo-induced thermochromic form prior to adark or thermal reverse reaction, and the reverse reaction may beinduced by the absorption of photons. This is particularly advantageousin optical switch and related ultrafast optical applications when a 1nanosecond or faster switching time for the forward and the reverse orback reactions is desired. Thermal cooling as the process for thereverse reaction typically occurs in a microsecond or longer. Incontrast, a photo-induced reverse reaction may be initiated andcompleted in less than 1 nanosecond after the photon absorption for theforward reaction and thus may occur while the heat-induced thermochromicform of the polydiacetylene is still present and has not significantlyreverted thermally to the starting polydiactetylene.

[0030] To provide the photo-induced reverse reaction, the absorption ofphotons may be by the organic free radical compound, by the heat-inducedthermochromic form of the polydiactetylene, by a photosensitizercompound added to the layer for the purpose of sensitizing this backreaction, or by combinations thereof. In one embodiment, the opticalshutter further comprises a photosensitizer compound and thephoto-induced reaction is sensitized by the photosensitizer compound.Preferably, the photo-induced reverse reaction is a sub-nanosecondphoto-induced electron transfer with a rapid, sub-nanosecond reversedark electron-transfer reaction, as known in the art of photo-inducedreversible electron transfer reactions. This results in the rapidformation of the starting organic free radical compound,polydiacetylene, and photosensitizer compound, if a photosensitizercompound is present, as they existed prior to the absorption of photonsfor the photo-induced thermochromic forward reaction. In one embodiment,the photo-induced reaction is a photo-induced reversible electrontransfer reaction.

[0031] In one embodiment of the optical shutter of the presentinvention, the photon absorption leading to the thermochromic change inabsorption is induced by ultraviolet radiation. In one embodiment, thephoton absorption is induced by visible radiation, and preferably isinduced by near-infrared radiation. In one embodiment, the absorption ofphotons is from a free radical ground state to an excited state of thefree radical compound. This is particularly important where the lowerexcited state corresponding directly to the free radical moiety groundstate of the free radical compound can not be efficiently populated byabsorption into another absorption band of the free radical compound,such as for example, into a π→π* aromatic absorption band due torelatively inefficient internal conversion from this excited state tothe lower excited state related to the free radical moiety. For example,absorption of laser radiation at 532 nm by IR-165 dye in a layer doesnot produce the efficient photo-induced heat transfer that occurs uponabsorption of laser radiation at 1065 nm. Suitable light sources forproviding the photons for the optical shutters of this invention are notlimited to lasers and may include a wide variety of other light sourcesknown in the art for providing high intensity (such as greater than 1mW) sources of photons such as, for example, a continuous or pulsedxenon lamp source with an external modulator and bandpass filters toprovide the desired wavelengths of irradiation for the desired timeintervals and durations of exposure to the photons.

[0032] In one embodiment of the optical shutter of this invention, theoptical shutter comprises a metallized layer on at least one side of alayer comprising the photon-absorbing compound and the reversiblethermochromic polydiacetylene compound of the optical shutter. In oneembodiment, the metallized layer comprises aluminum. Other suitablemetals include, but are not limited to, gold and silver. This metallizedlayer may serve a variety of functions, such as, for example, reflectingmore incident radiation back through the optical shutter layer,enhancing heat development in the optical shutter layer, and acting asan enhanced or a reduced reflective element in an optical switchcomprising the optical shutter of this invention. For example, theseenhanced or reduced reflective properties may result from the effect ofthe changes of absorption in the layer comprising the photon-absorbingcompound and polydiacetylene compound on the reflectivity of themetallized layer and may be utilized in a reversibletransparent-to-reflective optical shutter or optical gate in a fiberoptics communication channel as described, for example, in U.S. Pat.application Ser. No. 09/706,166, filed Nov. 3, 2000, titled “OpticalShutter”, by Carlson of the common assignee, the disclosures of whichare fully incorporated herein by reference.

[0033] One aspect of the present invention pertains to an opticalshutter comprising an organic radical cation compound and apolydiacetylene compound. In one embodiment, the polydiacetylenecompound is characterized by a change in absorption in a visible and/ora near-infrared wavelength region as a result of a photo-induced heattransfer from the radical cation compound. In one embodiment, theoptical shutter further comprises a radical anion.

[0034] Another aspect of this invention pertains to an optical shuttercomprising an organic radical anion compound and a polydiacetylenecompound. In one embodiment, the polydiacetylene compound ischaracterized by a change in absorption in a visible and/or anear-infrared region as a result of a photo-induced heat transfer fromthe radical anion compound. In one embodiment, the optical shutterfurther comprises a radical cation.

[0035] Another aspect of the present invention pertains to an opticalshutter comprising an organic free radical compound, preferably aradical cation compound or a radical anion compound, and a reversiblethermochromic polydiacetylene compound in which the polydiacetylenecompound is characterized by having a change in absorption in a visibleand/or near-infrared region as a result of a photo-induced heat transferfrom the free radical compound. In one embodiment, the optical shutteris utilized in an optical switch for a fiber optics communicationschannel. For example, an initial optical density of less than 0.1 orgreater than 80% transmission in the 1525 to 1575 nm region of interestfor the optical switch may be switched upon laser exposure and rapidconversion of photons to heat to an optical density of greater than 1.6or less than 2.5% transmission in less than 1 nanosecond and thenreversibly switched back upon cooling to the initial optical density inless than 1 second. The optical shutters of the present invention may beutilized as a reversible transparent-to-opaque optical shutter oroptical gate in a fiber optics communication channel, including in anoptical switch and in an optical modulator, as described, for example,in U.S. Pat. application Ser. Nos. 09/705,118 and 09/706,166, filed Nov.2, 2000, and Nov. 3, 2000, respectively, both titled “Optical Shutter”,to Carlson of the common assignee, the disclosures of which are fullyincorporated herein by reference.

[0036] In one embodiment, the optical shutter is utilized in a viewinglens of an eyewear device, such as, for example, in sunglasses. In oneembodiment, the optical shutter is utilized in a laser protection devicefor protection of eyes or sensors from a source of laser radiation. Inone embodiment, the optical shutter is utilized in a security protectionsystem based on detecting the change in absorption upon exposure of theoptical shutter in the security protection system to high intensityradiation selected from the group consisting of ultraviolet radiation,visible radiation, and infrared radiation. The high intensity radiationmay be produced by a pulsed laser which provides a unique lightintensity to trigger the optical shutter, which is not activated underambient room light and other conventional conditions. In addition to theabove product applications, the optical shutter of this invention may beutilized in a variety of other reversible imaging applicationsincluding, for example, reversible optical information recording.

[0037] The organic nature of the organic free radical compounds, thepolydiacetylenes, and the optical shutters of the present invention isadvantageous for ease of fabrication, such as by known methods ofcoating or plastic molding, in comparison to inorganic glass materialstypically used in all-optical or hybrid optical shutters and switches.

[0038] While the invention has been described in detail and withreference to specific and general embodiments thereof, it will beapparent to one skilled in the art that various changes andmodifications can be made therein without departing from the spirit andscope thereof.

1. An optical shutter comprising: (a) a photon-absorbing organic freeradical compound; and (b) a polydiacetylene compound; wherein saidpolydiacetylene compound is characterized by having a change inabsorption in a wavelength region as a result of a photo-induced heattransfer from said free radical compound.
 2. The optical shutter ofclaim 1 , wherein said free radical compound is a radical cation.
 3. Theoptical shutter of claim 2 , wherein said radical cation is an aminiumradical cation.
 4. The optical shutter of claim 2 , wherein said radicalcation is tris (p-butylaminophenyl) aminium hexafluoroantimonate.
 5. Theoptical shutter of claim 1 , wherein said free radical compound is aradical anion.
 6. The optical shutter of claim 5 , wherein said radicalanion is an anthrasemiquinone radical anion.
 7. The optical shutter ofclaim 1 , wherein said free radical compound is a radical cation, andwherein said optical shutter further comprises a radical anion.
 8. Theoptical shutter of claim 1 , wherein said free radical compound is aradical anion, and wherein said optical shutter further comprises aradical cation.
 9. The optical shutter of claim 1 , wherein saidpolydiacetylene compound comprises a metal salt.
 10. The optical shutterof claim 1 , wherein said change in absorption is greater than 0.1. 11.The optical shutter of claim 1 , wherein said change in absorption isgreater than 1.5.
 12. The optical shutter of claim 1 , wherein saidchange in absorption is greater than 3.0.
 13. The optical shutter ofclaim 1 , wherein said wavelength region is from 400 to 700 nm.
 14. Theoptical shutter of claim 1 , wherein said wavelength region is from 700to 1000 nm.
 15. The optical shutter of claim 1 , wherein said wavelengthregion is from 1000 to 1700 nm.
 16. The optical shutter of claim 1 ,wherein said wavelength region is from 1250 to 1600 nm.
 17. The opticalshutter of claim 1 , wherein said wavelength region is from 1520 to 1580nm.
 18. The optical shutter of claim 1 , wherein said photo-induced heattransfer occurs in less than 1 nanosecond after absorption of photons bysaid free radical compound.
 19. The optical shutter of claim 1 , whereinsaid photo-induced heat transfer occurs in less than 0.1 nanosecondsafter absorption of photons by said free radical compound.
 20. Theoptical shutter of claim 1 , wherein said photo-induced heat transferoccurs in less than 0.01 nanoseconds after absorption of photons by saidfree radical compound.
 21. The optical shutter of claim 1 , wherein saidphoto-induced heat transfer occurs in less than 0.001 nanoseconds afterabsorption of photons by said free radical compound.
 22. The opticalshutter of claim 1 , wherein said change in absorption is reversed bycooling to a temperature of less than 50° C.
 23. The optical shutter ofclaim 1 , wherein said change in absorption is reversed by cooling to atemperature of less than 75° C.
 24. The reversible shutter of claim 1 ,wherein said change in absorption is reversed by cooling to atemperature of less than 110° C.
 25. The optical shutter of claim 1 ,wherein said change in absorption is reversed in less than 1 secondafter said photo-induced heat transfer.
 26. The optical shutter of claim1 , wherein said change in absorption is reversed in less than 10milliseconds after said photo-induced heat transfer.
 27. The opticalshutter of claim 1 , wherein said change in absorption is reversed inless than 1 millisecond after said photo-induced heat transfer.
 28. Theoptical shutter of claim 1 , wherein said change in absorption isreversed in less than 0.1 milliseconds after said photo-induced heattransfer.
 29. The optical shutter of claim 1 , wherein said change inabsorption is reversed by a photo-induced reaction.
 30. The opticalshutter of claim 29 , wherein said optical shutter comprises aphotosensitizer compound and said photo-induced reaction is sensitizedby said photosensitizer compound.
 31. The optical shutter of claim 29 ,wherein said photo-induced reaction is a photo-induced reversibleelectron transfer reaction.
 32. The optical shutter of claim 1 , whereinsaid photo-induced heat transfer is induced by ultraviolet radiation.33. The optical shutter of claim 1 , wherein said photo-induced heattransfer is induced by visible radiation.
 34. The optical shutter ofclaim 1 , wherein said photo-induced heat transfer is induced bynear-infrared radiation.
 35. The optical shutter of claim 1 , whereinsaid photo-induced heat transfer is induced by absorption of photonsfrom a free radical ground state to an excited state of said freeradical compound.
 36. The optical shutter of claim 1 , wherein saidoptical shutter further comprises a metallized layer on at least oneside of a layer comprising said free radical compound and saidpolydiacetylene compound of said optical shutter.
 37. The opticalshutter of claim 33 , wherein said metallized layer comprises aluminum.38. An optical shutter comprising (a) a photon-absorbing organic freeradical compound; and (b) a polydiacetylene compound; wherein saidpolydiacetylene compound is characterized by having a change inabsorption in a wavelength region as a result of a photo-induced heattransfer from said free radical compound; and wherein said opticalshutter is utilized in an optical switch for a fiber opticscommunications channel.
 39. An optical shutter comprising: (a) aphoton-absorbing organic free radical compound; and (b) apolydiacetylene compound; wherein said polydiacetylene compound ischaracterized by having a change in absorption in a wavelength regionfrom 400 nm to 2000 nm as a result of a photo-induced heat transfer fromsaid free radical compound; and wherein said optical shutter is utilizedin a laser protection device for protection of eyes or sensors from asource of laser radiation.
 40. An optical shutter comprising: (a) aphoton-absorbing organic free radical compound; and (b) apolydiacetylene compound; wherein said polydiacetylene compound ischaracterized by having a change in absorption in a wavelength regionfrom 400 nm to 2000 nm as a result of a photo-induced heat transfer fromsaid free radical compound; and wherein said optical shutter is utilizedin a security protection system based on detecting said change inabsorption upon exposure of said optical shutter in said securityprotection system to high intensity radiation selected from the groupconsisting of ultraviolet radiation, visible radiation, and infraredradiation.
 41. An optical shutter comprising: (a) a photon-absorbingorganic free radical compound; and (b) a polydiacetylene compound;wherein said polydiacetylene compound is characterized by having achange in absorption in a visible wavelength region as a result of aphoto-induced heat transfer from said free radical compound; and whereinsaid optical shutter is utilized in a viewing lens of an eyewear device.42. An optical shutter comprising: (a) a photon-absorbing material,wherein said photon-absorbing material converts absorbed photons to heatin less than 1 nanosecond; and (b) a reversible thermochromicpolydiacetylene compound; wherein said polydiacetylene compound of saidoptical shutter changes its absorption at one or more wavelengths whenheated to a temperature greater than 50° C. and reversibly changes saidabsorption when subsequently cooled to a temperature less than 50° C.